Separation and segregation of a material from a liquid mixture by means of a solvent



March 11, 1947. ANTQNIO 2,417,048

SEPARATION AND SEGREGATION OF A MATERIAL FROM A LIQUID MIXTURE BY MEANS OF A SOLVENT Filed Feb. 27, 1942 zzrzncroa 2 AMMoM/A JTR/PPER.

I I u I v n i HEATER Patented Mer ll, 1941 s v I 2,417,048

UNITED- s'rArEs PATENT, .orrlca TERIAL FROM A LIQUID MIXTURE BY OF A SOLVENT v r Adolph L Antonio, Baton Rouge, La'., assignor,

by mcsne assignments, to J asco,-Incorporatcd, a corporation of Louisiana Applicatlon'Februar-yz'l, iaia'sei-lal No. 432,618

' 50mm. (or. 260-6815) 2 This invention relates to improvements in the introduced into upper part of extractor 3 through separation and concentration of a material from pipe 4 provided with valve 5. The liquid hydro a hydrocarbon mixture which is normally gaseous carbon mixture, and the copper solution pass in by the use of a solvent in which solvent atleast counter-current flow to each other in extractor.

two of the materials in the hydrocarbon mixture 5 3. This is preferably carried out at as low a temare soluble. perature as possible without freezing the copper Solvents have been used heretofore to separate solution, that is, not below -5 F. The hydro-- and extract a material from hydrocarbon mixcarbon mixture, after being contacted with the tures but where two or more materials are soluble copper solution, is removed from the top .of the and extracted in the same solvent, it has been extractor 3 by means of pipe 6 provided with valve the practice heretofore to obtain the separation I. It may be heat exchanged with the feedand of the desired'material by using a mixture of solwashed with water for the removal of entrained vents to separate the said material from the and soluble ammonia. hydrocarbon mixture. The difliculties hereto- The rich copper solution below the point where fore in this process were that there always was the feed is passed into the extractor 3 is consome of the undesirable material separated along tacted with recycle hydrocarbon liberated in a with the desired material. stripper l4 and introduced into the bottom of ex- For the sake of illustration and not as a limitractor 3 by means of pipe 8. The temperature tation, an extraction of butadiene 1,3 from a fracin the bottom of extractor 3 is maintained at tion of mixed hydrocarbons is herewith described about 20 F. The copper solution is withdrawn by the use .of an aqueous solution of cuprous from the extractor 3 by means of pipe ll, proacetate, ammonium acetate, and excess ammonia vided with pump I? and heater IS. The rich asthe solvent. The rich copper solution obtained copper solution'isiheated to a temperature preby contacting the solvent with the mixed hydroferablyin the range from about 55 to 65 F. at carbon feed contains a considerable percentage a pressure high enough to keep the hydrocarbons of butenes together with the butadiene; The in a liquid phase and is introduced into stripper percentage of butenes varies depending upon the M. Butenes and some butadiene are rejected percentage of butenes in the feed stock. From from this solutijon and passed through pipe 8 a feed stock containing butadiene and 70% which is also provided with pressure release valve butenes, the rich copper solution obtained by 30 I5 and returned tothe lower part of the extraccontacting the copper solution therewith, will tor 3. The copper solution introduced in the contain from 5 to 10% of butenes based on the upper part of the stripper H by pipe ll flows total hydrocarbons in the copper solution. downward in the stripper H in counter-current An object of this invention is to provide imflow to hydrocarbons rejected in the bottom of the provements in the solvent extraction of a spestripper l4. Some of the butadiene is absorbed cific material from a mixture of materials'that by the copper solution'dis'placing the butenes due are likewise soluble in a different degree in the to preferential absorption, thereby effecting an said solvent in orderthat a substantially pure or increase in the ratio of butadiene to butenes as- 98% to 100% concentration of the desired ma sociated with the copper solution phase. A porterial is obtained; I 40 tion or all of the copper solution may be with- Another object of this invention is to obtain a drawn from plate 44 through pipe l6, heated to substantially 100% yield in the separation and to F. by means-of heater l1, and returned concentration of the desired material. by means of pump l8 to the stripper l4 below These and other objects of the invention will' plate 44." The settled and disengaged copper be understood by reading the following descrip- 45 'solution in the bottom of this stripper will ,con-

tion with referenc to the diagrammatical flow tain essentially butadiene of 98' to 100% purity. sheet. The purity of the butadiene in the copper solu- According to this invention, butadiene in 9. tion removed from the extractor 3 will normally high state of purity is obtained from a mixture be in the range of to of butadiene, butane, butene-l, butene-2 and iso- 50 The copper solution leaving stripper I4 is then butylene. The hydrocarbon mixture is first conpassed by means of pipes I9, 20 and 2| provided densed and the liquid hydrocarbon mixture pass d with valves 22 and 23, and heater 24, to the dethrough pipe I provided with valve 2 to the lower sorber 25. A part of this stream may be heated part of extractor 3. A solution of cuprous acein the heater 24 and passed to the middle of the tate, ammonium acetate and excess ammonia is 55 desorber 25. A portion of the solution is passed prous salt solution inwhich to the upper part of the desorber 26 through the line 2|. The solution is heated to a temperature of about 150 to 180 F. by means of a steam coil 26 in the lower part of the desorber 26 and the desorbed hydrocarbons are removed through pipe 27. The copper solution relatively free of hydrocarbons is removed through line 28 provided with valve 29 and may be recycled after being refortifi d if necessary to extractor 3.

The butadlene vapors removed from desorber 25 through pipe 21 are passed through washer 36 where water is provided through pipe 3! to scrub out the ammonia. The butadiene vapors are removed through pipe 32 provided with valve 38 and passed to storage (not shown). The water used for scrubbing the butadiene is passed through pipe 34, provided with valve I5, pump 36 and heater 31 into an ammonia stripper 36 where it is heated by means of direct steam, introduced through pipe 39 and the overhead vapors are passed through pipe 40 to recover ammonia of 95 to 160% concentration and to 0% water. This ammonia may be used to fortify the cuprous solution and maintain the desired concentration. The water is removed, through pipe 42 provided with valve 43.

Alternately the absorption and stripping may I be carried out in one tower by maintaining the temperature in the lower part of the tower sufllciently high to partially strip the rich copper solution of a part of the solutes as it passes through the lower part of the'tower, the liquid dioiefins being then reabsorbed as they pass in countercurrent flow to the copper solution.

Likewise a part of the diolefins obtained from the desorber may be liquefied and recycled to the lower part of the stripper. when the diolefins are used in the manufacture of rubber, a portion in time accumulates such a concentration of impurities that they are no longer suitable for the manufacture of rubber. These impure portions of the dioleflns may be purified by passing into the stripper or the absorber.

In order to illustrate the process, packed towers the second expelled hydrocarbon into contact with the solution just before heating in the second step to strip it and finally heating the residual solution to obtain diolefin.

2. A process for the separation and segregation of a diolefin from a hydrocarbon mixture containing a diolefin and a mono-olefin according to claim 1 in which the contacting temperature for contacting the solvent with the mixture of gases is not below -5 F.

3. A process for the separation and segregation of a diolefin from a hydrocarbon mixture containing a diolefin and a mono-olefin according to claim 1 in which the first temperature in the first heating step is 55-65 F.

4. A process for the separation and segregation of a diolefin from a hydrocarbon mixture containing a diolefin and a mono-olefin according to claim 1 in which the temperature in the second heating step ranges from about 65 to 85 F.

5. A process for the separation and segregationot a diolefin from a hydrocarbon mixture containing a diolefin and a mono-olefin accordin to claim 1 in which the cuprous salt solution is a solution of cuprous acetate, ammonium acetate 46 and an excess of ammonia.

are shown but other towers provided with plates,

bell caps, etc., may be used.

Turbo mixers with intervening settling chambers may likewise be used in absorption of the dioleflns with the copper solution and by changing the temperature and pressure, the turbo mixers with intervening settling chamber may also be used to fractionally separate thediolefins from the'copper solution.

I claim:

1. A processfor the separation and segregation 65 Number of a diolefin from a hydrocarbon mixture containing a diolefin and a mono-olefin which comprises contacting a mixture oihydrocarbons containing a diolefin and a mono-olefin with a cu- ADOLPH L. ANTONIO.

REFERENCES CITED UNITED STATES PATENTS Number Name Date 2,154,676 Haeuber et al. Apr. 18, 1939 1,977,659 Watts Oct. 23, 1934 2,275,135 Fasce Mar. 3, 1942 2,188,899 Hebbard et a1. Feb. 6, 1940 FOREIGN PATENTS Country Date 390,863

OTHER REFERENCES Lur'e et al., Sinteticheskii Kauchuk, No. 619-29,

the diolefin is more (1934).

Britain Apr. 13, 1933- 

